Coupling components for azo dyestuffs



United States Patent COUPLING COMPONENTS FOR AZO DYESTUFFS Jack L.Towle, East Cleveland, and William H. Meek, Jr.,

Sagamore Hills, Ohio, assignors-to Kewanee Oil Company, Bryn Mawr, Pa.,a corporation of Delaware No Drawing. Filed Dec. 19, 1966, Ser. No.602,554

6 Claims. (Cl. 260-558) This invention relates to new and novel organiccompounds and more particularly to .compounds that are useful ascoupling components in the syntheses of azo disperse dyes.

The new compounds of the present invention can be defined by thefollowing general formula:

CHZCHrti-N 1 (cmnon .OHa N\ 0 1 1 crnom-ii-N-cmcrnon CZECHp-N-CHzCHgOHCHzCHzOH 3,417,139 Patented Dec. 17, 1968 CHzCHzC-C I lCHzCHaC-N-CHaCHICHaOH /C:Hs Q-N o CHICHZOH II According to the presentinvention these new coupling components can be prepared by reactingprimary or secondary aliphatic amines containing terminal hydroxy groupswith variously substituted N-B-carboalkoxyethylanilines as shown in thefollowing reaction:

| Q-Ik-CEIzCHziL-N-CHzCHzOH OHaOH When reacted with suitable diazotizedamines these new compounds form dyestuffs which possess very desirableproperties such as brightness, resistance to gas-fading,dischargeability and good build-up on fibers such as acetate,triacetate, polyamide and polyester.

This invention will be more fully described by the following examples.The inventionis not to be regarded, however, as restricted in any way bythese examples and they are to serve merely as illustration. In theseexamples and throughout the specification, parts and percentages aregiven inn/eight unless specifically provided otherwise.

EXAMPLE I To a 1-liter three-neck flask equipped with a stirrer,thermometer, reflux condenser, and an oil bath are charged 242.0 g. ofN-ethylaniline (2.0 moles), 190.0 g'. of methyl acrylate (2.2 moles),and 30.0 g. of glacial acetic acid. The mixture is heated at C. for 72hours and then fractionated under reduced pressure with a nitrogenbleed. The first fraction contains acetic acid and unreacted methylacrylate which coclistil at 2835 C. and 50 mm. Hg. A second fraction of15.0 g. of N-ethylaniline, boiling at 62-7 C. at 5 mm. Hg is collected.A third fraction weighing 352.0 g. of N-eth'yl-N-s-carbomethoxy-ethylaniline (85% of theory) boiling at 1l2-14 C. and 1mm. Hg is collected.

A mixturev of 62.2 g. of N-ethyl-N-B-carbomethoxyethylaniline (0.3 mole)and 36.8 g. of ethanolamine (0.6 mole) was charged to a 250 ml.three-neck flask equipped with a magnetic stirrer, a thermometer, and areflux condenser with a Dean-Sark trap. By means ofan oil bath, themixture was heated slowly to a maximum temperature of C. During thisperiod 9 ml. of methanol was collected. After heating the mixture forone hour at 150 C. the excess ethanolamine was distilled to a maximumhot temperature of 150 C. at 15 mm. Hg. By this method was obtained 68.7g. (97% of theoretical of N- ethyl-N-fi-'[N"-(fl'-hydroxyethyl)]carbamylethylaniline. I. 02115 l OHzCHr-ii-N-CHnCHzOH CHzCHaC-N CHzCHzOH(IV) N ethyl-N-fi-[N'-ethyl-N'-('y-hydroxypropyl) ]carbamylethylaniline.

\ II CHaGHzCN CHIGHrCHzOH (V) N-ethyl-N-p- [N,N'-bis fi'-hydroxyethyl)]carb amyl ethylaniline.

CaHr

Compounds I to V when coupled with amine components such as2-amino-5-nitrothiazole and 2-arnino-6- methylsulfonylbenzothiazole formblue, violet, or cerise dyes. These dyes are found to have hightinctorial strength, superior sublimation properties and excellentgasfastness and dischargeability.

The synthesis of a typical dyestuff incorporating one of the novelcomponents of this invention can be effected according to the followingprocedure:

CHzCHzOH Diazotization Nitrosyl sulfuric acid is prepared by theportionwise addition of 6.9 g. of sodium nitrite (0.1) mole to 45.6 ml.of 96% sulfuric acid at a rate to keep the temperature below 70 C. Thesolution is cooled to 10 C. and a mixture of 77.0 ml. of acetic acid and14.0 ml. of propionic acid is added in portions at l-l5 C.

The resulting solution is cooled to 0 C. and 14.5 g. of2-amino-5-nitrothiazole (0.1 mole) is added in portions over /2 hour at0-3 C. After stirring for A hour a mixture of 77.0 ml. of acetic acidand 14.0 ml. of propionic acid is added slowly at 0-5 C. The solution isstirred for /2 hour at 0 C. after which any excess nitrite is destroyedwith urea.

Coupling A solution of 23.6 g. of N-ethyl-N-,3-[N'-(B'-hydroxyethyl)]carbamylethylaniline (0.1 mole) in 104.5 ml. of acetic acid and 166.0ml. of propionic acid is cooled to 0 C. The cold diazonium solution isadded in small portions over hour at 0-3 C. After stirring for A houranhydrous sodium acetate is added slowly until neutral to Congo red testpaper. The viscous solution is stirred for hour at 0 C. and then pouredinto 2 liters of ice water with vigorous stirring. The precipitated dyeis collected on a Biichner funnel and washed with fresh water to removeacid and other soluble impurities.

The product is a violet dye that builds well on acetate, triacetate,polyester and nylon.

While certain features of this invention have been described in detailwith respect to various embodiments thereof, it will, of course, beapparent that other modification may be made within the spirit and scopeof this invention and it is not intended to limit the invention to theexact details shown above except insofar as they are defined in thefollowing claims.

The invention claimed is:

1. A compound having the formula:

(CHaMOH where R is hydrogen or a methyl radical; R is an alkyl radicalhaving 1-6 carbon atoms; R is selected from the group consisting ofhydrogen, an alkyl radical having 1-6 carbon atoms and ahydroxy-terminated alkyl radical of from 2-6 carbon atoms, and n is aninteger having a value of at least 2 and no more than 6.

2. A compound of claim 1 having the formula:

CH3 3. A compound of claim 1 having the formula /C:II5 Q- CHICHIOH 4. Acompound of claim 1 having the formula CHzCHaCHiOH 5. A compound ofclaim 1 having the formula OHaCHr-C-N 6. A compound of claim 1 havingthe formula CaHe N\ CHQGHIOH CHzCHa--CN II CHaCHr-G-N References CitedUNITED STATES PATENTS 3,189,646 6/1965 Rainer 260-558 HENRY R. IILES,Primary Examiner.

H. I. MOATZ, Assistant Examiner.

US. Cl. X.R.

